VINYL CHLORIDE PRODUCTION PROCESS

Abstract: A method for the production of VCM by catalytic oxychlorination of ethane wherein HCl is supplied in excess of the stoichiometric requirement for chlorine in the reaction.

Description: VINYL CHLORIDE PRODUCTION PROCESS The present invention relates to a process for the production of vinyl chloride monomer (VCM) from ethane via oxychlorination of ethane. More particularly, the invention relates to a method for controlling the selectivity of the oxychlorination of ethane. VCM is most commonly produced from ethylene and chlorine feeds by chlorinating ethylene to produce 1,2-dichloroethane and subsequently dehydrochlorinating this intermediate to yield VCM. The cost of ethylene is a significant contribution to the final cost of VCM produced by this method. Accordingly, interest has been shown in alternative hydrocarbon feeds in VCM production. A prime candidate for an alternative hydrocarbon from which VCM may be produced is ethane. Not only is ethane cheaper than ethylene, but the chemistry of its conversion to VCM has distinct advantages. For example, the favoured oxychlorination reaction is a single step process in which ethane can be directly converted to VCM: C 2 H 6 + Cl + 0 2 → C 2 H 3 C1 + other products + H 2 0 The chlorine source may be provided in the form of Cl 2 gas, hydrogen chloride or a chlorinated hydrocarbon. The selectivity of this reaction to VCM in favour of the "other products" is not total and is a source of inefficiency in the oxychlorination process. Other products may include recyclable intermediates such as ethylene and 1,2-dichloroethane, which may ultimately be converted to VCM. However, an appreciable percentage of these other products comprises burning products (mainly C0 2 ) which result from oxidation of ethane in an uncontrolled manner. Such products cannot be economically recycled in the VCM production process and represent wastage of raw material. The selectivity of the oxychlorination reaction towards VCM and, most importantly, away from the burning products may be improved in a number of ways. A number of catalysts have been proposed in the art which affect the selectivity of the oxychlorination reaction. For example, GB 1492945 (BP) discloses the use of a Copper/Potassium/Cerium catalyst for the oxychlorination of ethane. However, the product spectrum quoted in the results is incomplete, with up to 18% of the ethane feed unaccounted for. Furthermore, the ethane feed is diluted with Nitrogen to an impractical degree. In our copending United Kingdom Patent Application No. 9318501.5, filed contemporaneously herewith, we disclose a novel catalyst for catalysation of the oxychlorination reaction. A full spectrum of by-products is given in the examples of this application. We have now developed a new and different technique for the reduction of the amount of burning products generated during the oxychlorination reaction. The technique may be used in any oxychlorination process, for example that described in our copending United Kingdom Patent Application No. 9318497.6, filed contemporaneously herewith, in conjunction with any catalyst. According to a first aspect of the present invention, there is provided a method for the production of VCM by catalytic oxychlorination of ethane wherein HCl is supplied in excess of the stoichiometric requirement for chlorine in the reaction. The HCl may be the only source of chlorine in the oxychlorination reaction. Alternatively, it may be supplied together with a second chlorine source, such as a chlorinated hydrocarbon or chlorine itself. All the chlorine requirement may be supplied by the second chlorine source. In general, the greater the excess of HCl supplied over its stoichiometric requirement the greater the beneficial effect on the selectivity of the oxychlorination reaction. Where there is no requirement for HCl, because all the chlorine requirement is supplied in an alternative form, any quantity of HCl which is added will have a beneficial effect. The ratio of HCl to ethane used in the reaction is preferably in the range 0.1 to 10 on a molar basis, and advantageously in the range 0.5 to 3. Because not all the HCl is consumed in the reaction, HCl will leave the reactor together with the products of the reaction. Preferably, the excess HCl is recycled to the reactor. Recovery of the HCl in order to recycle it may be accomplished by any conventional means known in the art. According to a second aspect of the present invention, there is provided the use of HCl in excess of its stoichiometric requirement for the enhancement of the selectivity of the catalytic oxychlorination of ethane in the production of VCM. The invention may be used in any catalytic oxychlorination process. Preferably, the catalyst used in conjunction with the invention is a copper-based catalyst. Advantageously, this catalyst may further comprise an alkali metal and a lanthanide element, > such as Potassium and Cerium respectively. A preferred catalyst is described in our copending United Kingdom Patent Application No. G12134P, filed contemporaneously herewith. The reaction conditions employed may be any suitable conditions known in the art. Preferred conditions are set out in our copending United Kingdom Patent Application No. G12468P, filed contemporaneously herewith. The invention will now be described for the purposes of illustration only with reference to the following examples. Example 1 A catalyst containing 1.3% copper and 3.4% potassium was prepared by evaporation of an aqueous solution of the metal chlorides onto an Alumina carrier. To a 250 cm 3 sample of de-ionised water was added 20g of CuCl 2 .2H 2 0 and 35g of KCl. The resultant solution was added stepwise to 500g of catalyst carrier (Type SAHT-99, Production Chemicals Ltd.) . This catalyst paste was dried by heating to 120°C for 24 hours and then sieved to break up agglomerates before use. When prepared, the catalyst was found to have a surface area of lm 2 /g and to have a mean particle size of 90 microns. A catalyst charge of 400cm 3 was loaded into a 50.8mm diameter Inconel fluidised bed reactor to give a bed length of approximately 40cm. The conversions and selectivity achieved by the catalyst was measured using an on-line gas chromatograph. The reactor was heated electrically to the desired operating temperature and a reactor feed consisting of ethane, hydrogen chloride, nitrogen and oxygen was used. The feed details together with the results are shown as example 1, table 1. Example 2 Using the same catalyst as example 1 the reactor was operated under the same conditions except with an increased hydrogen chloride flow and without a nitrogen flow. The results are displayed in table 2. In example 2, the excess hydrogen chloride supplied was not able to take part in the oxychlorination reaction as all of the oxygen has been consumed at the lower hydrogen chloride flow rate shown in example 1. It is seen from the table that by increasing the flow of hydrogen chloride to the reactor, the yield to burning products (mainly C0 2 ) decreases from 8.44 to 7.27% of the ethane reacted. Example 3 Using a catalyst of the same composition as that in example 1 and utilising a mixed chlorohydrocarbon feed, the effect of increasing the hydrogen chloride flow is shown as example 3A to 3C, table 2. Example 4 Again using catalyst of the same composition as in example 1 and utilising a mixed chlorohydrocarbon feed, the effect of increasing the hydrogen chloride flow but at a higher temperature than example 2 is shown as example 4A to 4C, table 2. Example 5 Again using catalyst of the same composition as in example 1 and utilising a mixed chlorohydrocarbon feed, the effect of increasing the hydrogen chloride flow but at a higher temperature than example 2 and a lower oxygen flow is shown as example 5A to 5C, table 2. Table 2 shows that under the three combinations of temperature and oxygen flow used, an increasing hydrogen chloride flow results in a decrease in the ethane burning rate. Furthermore, the efficiency with which ethane is converted within the reactor also increases as the hydrogen chloride flow to the reactor is increased. TABLE 1 (NOTES: A-All 3 isomers, B-l, 1 isomer, C - 1, 2 isomer, D -1, 1,2 isomer) TABLE 2 (NOTES: A-All 3 isomers, B-l, 1 isomer, C - 1, 2 isomer, D -I, 1,2 isomer)

Claims: CLAIMS : 1. A method for the production of VCM by catalytic oxychlorination of ethane wherein HCl is supplied in excess of the stoichiometric requirement for chlorine in the reaction. 2. The method of claim 1 wherein the HCl is supplied together with an additional chlorine source. 3. The method of claim 1 or claim 2 wherein the ratio of HCl to ethane in the reaction is between 0.1 and 10. 4. The method of claim 3 wherein the ratio of HCl to ethane in the reaction is between 0.5 and 3. 5. The method of any preceding claim wherein excess HCl exhausted from the reactor is recycled to the reactor. 6. The use of HCl in excess of its stoichiometric requirement for the enhancement of the selectivity of the catalytic oxychlorination of ethane in the production of VCM.

Inventors: CLEGG IAN MICHAEL, HARDMAN RAY, CLEGG, IAN, MICHAEL, HARDMAN, RAY
Applicants: CLEGG IAN MICHAEL, EVC TECH AG, HARDMAN RAY, CLEGG, IAN, MICHAEL, EVC TECHNOLOGY AG, HARDMAN, RAY
Application year: 1994
Main classification: C07C17
IPC codes: C07C17